Non-inflammable, anti-electrostatic polycarbonate molding materials

ABSTRACT

The present invention relates to anti-electrostatic polycarbonate compositions which are provided with chlorine- and bromine-free flame resistance and are distinguished by good mechanical and thermal properties and problem-free processability in the injection moulding process, i.e. by a good melt flowability and a low tendency towards juicing. The present invention also relates to the use of the polycarbonate moulding compositions according to the invention for the production of shaped articles and mouldings of all types, and the shaped articles and mouldings themselves.

[0001] The present invention relates to impact-modified polycarbonatemoulding compositions with antistatic properties which are provided withchlorine- and bromine-free flame resistance and are distinguished bygood mechanical and thermal properties and a problem-free processabilityin the injection moulding process.

[0002] Impact-modified polycarbonate moulding compositions which areprovided with chlorine- and bromine-free flame resistance are known.

[0003] EP-A 0 345 522 describes polymer mixtures of aromaticpolycarbonate, ABS graft polymer and/or styrene-containing copolymerwhich are provided with flame resistance with monophosphoric acidesters.

[0004] U.S. Pat. Nos. 5,204,394 and 5,672,645 describe PC/ABS mouldingcompositions which are provided with flame resistance by oligophosphoricacid esters or mixtures of oligo- and monophosphoric acid esters.

[0005] JP-A 111 997 68 describes PC/ABS blends which are provided withflame resistance with monomeric and oligomeric phosphoric acid esters,the flame resistance being improved significantly by addition of aninorganic filler, such as e.g. talc.

[0006] U.S. Pat. No. 5,849,827 describes PC/ABS moulding compositionswhich are provided with flame resistance with resorcinol-basedoligophosphate, the after-burning times being reduced significantly byaddition of nanoscale inorganic materials in low concentrations. WO99/07782 describes PC/ABS moulding compositions with a specificoligophosphate derived from bisphenol A and synergistic amounts of ananoscale inorganic compound.

[0007] Most plastics, thus also the moulding compositions described inthe patents and patent applications mentioned so far, are electricalinsulators with a high surface electrical resistance. Electricalcharging of the surface of the plastic, which easily arises duringprocessing of the material, by contact with other materials or byfriction, is therefore dissipated only extremely slowly and leads todiverse disturbances and trouble in practice, in particular to a rapidcontamination and dusting of the components of plastic with thedevelopment of undesirable characteristic dust figures.

[0008] The surface resistance and the dust-attracting tendency ofplastics can be reduced by additive treatment with so-calledantistatics. Commercially available additives for anti-electrostatictreatment of plastics which are employed are, for example, alkyl- andarylsulfonates, ethoxylated alkylamines, quaternary ammonium andphosphonium salts and fatty acid esters (see e.g. A. Lichtblau,“Antistatika”, Kunststoffe 86 (1996), 7, p. 955-958 and EP-A 0 897 950).The use of specific polyalkylene ethers/polyalkylene glycols foranti-electrostatic treatment of plastics is also described in the patentliterature.

[0009] DE-A 1 297 341 discloses, for example, a process for antistatictreatment of polymers which are built up exclusively or predominantlyfrom carbon and hydrogen (in particular polyethylene) by surfacetreatment with or incorporation of polyalkylene glycols.

[0010] FR-B-1 239 902 describes the use of ethylene oxide/propyleneoxide triple-block copolymers for antistatic treatment of polymers. Thetriple-block copolymers are said to display their antistatic action inpolymethyl methacrylate, PVC, polyethylene, polystyrene and ABS mouldingcompositions.

[0011] DE-A1-1 981 7993 describes ABS plastics which are provided withantistatic properties with specific triple-block copolymers of theformula X—Y—X with a central block Y of propylene oxide units andterminal blocks X of ethylene oxide units. The average content ofethylene oxide units in these triple-block copolymers here is 2 to 35wt. %.

[0012] DE-A-1 244 398 describes the use of polypropylene glycol as anantistatic for ABS resins. However, to achieve a significant effectpolypropylene glycol must be employed in large amounts (typically e.g. 5wt. %), which can lead to flecked and smeared surfaces of the finishedcomponents up to surface deposits on the finished components of plasticand/or in the injection mould.

[0013] PC/ABS moulding compositions comprising polyalkyleneethers/polyalkylene glycols are also known.

[0014] EP-A-0 135 801 describes impact-modified polycarbonate mouldingcompositions which are treated with 0.1 to 3 wt. %, based on the PC/ABSmatrix, of triple-block copolymers of the formula X—Y—X with a centralblock Y of propylene oxide units and terminal blocks X of ethylene oxideunits. The effect of the triple-block copolymers which is described inthis Application is to improve the processing properties of the mouldingcompositions in the injection moulding process, characterized by themould release properties, flowability and weld line strength, withoutimpairing the mechanical properties of the material.

[0015] EP-A-0 278 348 describes PC/ABS moulding compositions which areprovided with antistatic properties using specific polyalkylene ethers.The polyalkylene ethers used were modified here by treatment withsubstances which form free radicals, which increases their efficiency asan antistatic.

[0016] The PC/ABS moulding compositions with polyalkylene ethersdescribed in the abovementioned patent applications are indeeddistinguished by anti-electrostatic properties, but are notflame-resistant in the form described. However, for many uses flameresistance is necessarily required and antistatic properties areadditionally desired. Simultaneous anti-electrostatic andflame-resistant treatment of PC/ABS moulding compositions, however,proves to be extremely difficult, since the antistatics which can beused are in general readily combustible and their addition to themoulding composition is counter-productive to flame-resistant treatmentthereof by making it more difficult.

[0017] EP-A-0 979 840 describes antistatic and flame-resistantpolycarbonate moulding compositions which comprise an impact-modifiedpolystyrene and are provided with flame resistance with monomeric oroligomeric phosphoric acid esters and with antistatic properties withspecific sodium dodecylbenzenesulfonates. The moulding compositions canoptionally also comprise, inter alia, polyalkylene glycols.Polycarbonate moulding compositions with ABS are not described here.However, because of the poorer compatibility of the polymer components,compared with PC/ABS blends, the PC/HIPS blends described in EP-A-0 979840 prove to be problematic in respect of the flow line strength andtherefore the processability in the injection moulding process, inparticular in the production of thin-walled finished components ofinvolved structure, for which several gates are necessary to achievecomplete filling of the injection moulds.

[0018] U.S. Pat. No. 4,920,166 solves the problem of a simultaneousflame-resistant and antistatic treatment of PC/ABS by adding to thepolymer moulding composition on the one hand polyalkylene glycols whichhave been reacted with agents which form free radicals, as theantistatic, and on the other hand monophosphoric acid esters as an FRadditive and Teflon as an antidripping agent. Low molecular weightorganic bromine compounds can optionally also additionally be employedas an FR additive. The moulding compositions described do not have anadequate heat distortion point for many uses and during processing inthe injection moulding process tend markedly towards “juicing”, i.e.bleeding of volatile constituents of the moulding composition (inparticular the FR additive), and associated with this undesirableformation of a deposit on the injection mould surface.

[0019] The object of the present invention was to provide mouldingcompositions which are provided with anti-electrostatic properties andchlorine-/bromine-free flame resistance, have good mechanical andthermal properties, in particular high heat distortion points andnotched impact strengths, and are distinguished by good processabilityin the injection moulding process, the latter requiring excellentflowability (low melt viscosity) and a low tendency towards theformation of a deposit in the mould by bleeding of volatile constituentsof the moulding composition.

[0020] It has now been found that impact-modified polycarbonatecompositions which comprise specific polyalkylene ethers andhalogen-free phosphorus compounds of low volatility fulfil the requiredprofile of requirements.

[0021] The present invention therefore provides polycarbonatecompositions comprising

[0022] aromatic polycarbonate or polyester-carbonate,

[0023] at least one impact modifier,

[0024] at least one halogen-free phosphorus compound chosen from thesubstance groups of oligomeric phosphoric acid esters,phosphonate-amines and phosphazenes and

[0025] a polyalkylene ether compound based on propylene oxide or basedon propylene oxide and ethylene oxide, the propylene oxide contentbeing >60 wt. %, preferably ≧70 wt. % (based on the mass of thepolyalkylene ether).

[0026] The moulding compositions can optionally furthermore comprise

[0027] fluorinated polyolefin,

[0028] finely divided inorganic material,

[0029] further polymer components and

[0030] further commercially available polymer additives.

[0031] Preferred moulding compositions comprise

[0032] A) 30 to 98 parts by wt., preferably 40 to 95 parts by wt.,particularly preferably 50 to 90 parts by wt. of aromatic polycarbonate,

[0033] B) 0.5 to 50, preferably 1 to 35, particularly preferably 2 to 25parts by wt. of at least one graft polymer,

[0034] C) 0.5 to 40, preferably 1 to 30, in particular 2 to 20 parts bywt. of at least one halogen-free phosphorus compound chosen from thesubstance groups of oligomeric phosphoric acid esters,phosphonate-amines and phosphazenes,

[0035] D) 0 to 5, preferably 0.1 to 1, in particular 0.1 to 0.5 part bywt. of fluorinated polyolefin,

[0036] E) 0 to 50 parts by wt., preferably 1 to 30 parts by wt., inparticular 2 to 25 parts by wt. of vinyl (co)polymer and/or polyalkyleneterephthalate,

[0037] F) 0 to 10 parts by wt., preferably 0 to 5 parts by wt., inparticular 0 to 3 parts by wt. of finely divided inorganic material inthe form of particles, flakes or fibres,

[0038] G) 0 to 20, preferably 0 to 10, in particular 0 to 5 parts by wt.of at least one commercially available polymer additive and

[0039] H) 0.05 to 5, preferably 0.1 to 4, in particular 0.5 to 3 partsby wt. of polyalkylene ether based on propylene oxide or based onpropylene oxide and ethylene oxide, the propylene oxide content being≧60 wt. %, preferably ≧70 wt. % (based on the mass of the polyalkyleneether).

[0040] The sum of the parts by weight of all the components (A to H andoptionally further constituents) here is 100.

[0041] Very particularly preferred polycarbonate compositions aredistinguished in that they comprise as component H polyalkylene etherswith a number-average molecular weight of ≧2,000 g mol⁻¹, preferably≧3,000 g mol⁻¹, in particular ≧3,500 g mol⁻¹.

[0042] Component A

[0043] Aromatic polycarbonates and/or aromatic polyester-carbonatesaccording to component A which are suitable according to the inventionare known from the literature or can be prepared by processes known fromthe literature (for the preparation of aromatic polycarbonates see, forexample, Schnell, “Chemistry and Physics of Polycarbonates”,Interscience Publishers, 1964 and DE-AS 1 495 626, DE-A 2 232 877, DE-A2 703 376, DE-A 2 714 544, DE-A 3 000 610 and DE-A 3 832 396; for thepreparation of aromatic polyester-carbonates e.g. DE-A 3 077 934).

[0044] Aromatic polycarbonates are prepared e.g. by reaction ofdiphenols with carbonic acid halides, preferably phosgene, and/or witharomatic dicarboxylic acid dihalides, preferably benzenedicarboxylicacid dihalides, by the phase boundary process, optionally using chainterminators, for example monophenols, and optionally using branchingagents which are trifunctional or more than trifunctional, for exampletriphenols or tetraphenols.

[0045] Diphenols for the preparation of the aromatic polycarbonatesand/or aromatic polyester-carbonates are preferably those of the formula(I)

[0046] wherein

[0047] A is a single bond, C₁-C₅-alkylene, C₂-C₅-alkylidene,C₅-C₆-cycloalkylidene, —O—, —SO—, —CO—, —S—, —SO₂—, C₆-C₁₂-arylene, towhich further aromatic rings optionally containing heteroatoms can befused,

[0048] or a radical of the formula (II) or (III)

[0049] B in each case is C₁-C₁₂-alkyl, preferably methyl,

[0050] x in each case independently of one another, is 0, 1 or 2 and

[0051] p is 1 or 0, and

[0052] R⁵ and R⁶ can be chosen individually for each X¹ andindependently of one another denote hydrogen or C₁-C₆-alkyl, preferablyhydrogen, methyl or ethyl,

[0053] X¹ denotes carbon and

[0054] m denotes an integer from 4 to 7, preferably 4 or 5, with theproviso that on at least one atom X¹, R⁵ and R⁶ are simultaneouslyalkyl.

[0055] Preferred diphenols are hydroquinone, resorcinol,dihydroxydiphenols, bis-(hydroxyphenyl)-C₁-C₅-alkanes,bis-(hydroxyphenyl)-C₅-C₆-cycloalkanes, bis-(hydroxyphenyl) ethers,bis-(hydroxyphenyl) sulfoxides, bis-(hydroxyphenyl) ketones,bis-(hydroxyphenyl) sulfones andα,α-bis-(hydroxyphenyl)-diisopropyl-benzenes.

[0056] Particularly preferred diphenols are 4,4′-dihydroxydiphenyl,bisphenol A, 2,4-bis(4-hydroxyphenyl)-2-methylbutane,1,1-bis-(4-hydroxyphenyl)-cyclohexane,1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane,4,4′-dihydroxydiphenyl sulfide and 4,4′-dihydroxydiphenyl sulfone.

[0057] 2,2-Bis-(4-hydroxyphenyl)-propane (bisphenol A) is particularlypreferred.

[0058] The diphenols can be employed individually or as any desiredmixtures.

[0059] The diphenols are known from the literature or are obtainable byprocesses known from the literature.

[0060] Suitable chain terminators for the preparation of thethermoplastic aromatic polycarbonates are, for example, phenol andp-tert-butylphenol, and also long-chain alkylphenols, such as4-(1,3-tetramethylbutyl)-phenol according to DE-A 2 842 005 ormonoalkylphenols or dialkylphenols having a total of 8 to 20 C atoms inthe alkyl substituents, such as 3,5-di-tert-butylphenol,p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol and2-(3,5-dimethylheptyl)-phenol and 4-(3,5-dimethylheptyl)-phenol. Theamount of chain terminators to be employed is in general between 0.5 mol% and 10 mol %, based on the molar sum of the particular diphenolsemployed.

[0061] The thermoplastic aromatic polycarbonates can be branched in aknown manner, and in particular preferably by incorporation of 0.05 to2.0 mol %, based on the sum of diphenols employed, of compounds whichare trifunctional or more than trifunctional, for example those withthree or more phenolic groups.

[0062] Both homopolycarbonates and copolycarbonates are suitable. Toprepare copolycarbonates according to the invention according tocomponent A, 1 to 25 wt. %, preferably 2.5 to 25 wt. % (based on thetotal amount of diphenols to be employed), of polydiorganosiloxanes withhydroxy-aryloxy end groups can also be employed. These are known (see,for example, U.S. Pat. No. 3,419,634) or can be prepared by processesknown from the literature. The preparation of copolycarbonatescomprising polydiorganosiloxanes is described e.g. in DE-A 3 334 782.

[0063] Preferred polycarbonates are, in addition to the bisphenol Ahomopolycarbonates, the copolycarbonates of bisphenol A with up to 15mol %, based on the molar sum of diphenols, of other diphenols mentionedas preferred or particularly preferred.

[0064] Aromatic dicarboxylic acid dihalides for the preparation ofaromatic polyester-carbonates are preferably the di-acid dichlorides ofisophthalic acid, terephthalic acid, diphenyl ether-4,4′-dicarboxylicacid and naphthalene-2,6-dicarboxylic acid.

[0065] Mixtures of the di-acid dichlorides of isophthalic acid andterephthalic acid in a ratio of between 1:20 and 20:1 are particularlypreferred.

[0066] A carbonic acid halide, preferably phosgene, is additionallyco-used as a bifunctional acid derivative in the preparation ofpolyester-carbonates.

[0067] Possible chain terminators for the preparation of the aromaticpolyester-carbonates are, in addition to the monophenols alreadymentioned, also chlorocarbonic acid esters thereof and the acidchlorides of aromatic monocarboxylic acids, which can optionally besubstituted by C₁-C₂₂-alkyl groups, as well as aliphaticC₂-C₂₂-monocarboxylic acid chlorides.

[0068] The amount of chain terminators is in each case 0.1 to 10 mol %,based on the moles of diphenols in the case of the phenolic chainterminators and on the moles of dicarboxylic acid dichlorides in thecase of monocarboxylic acid chloride chain terminators.

[0069] The aromatic polyester-carbonates can also comprise incorporatedaromatic hydroxycarboxylic acids.

[0070] The aromatic polyester-carbonates can be either linear orbranched in a known manner (for this see also DE-A 2 940 024 and DE-A 3007 934).

[0071] Branching agents which can be used are, for example, carboxylicacid chlorides which are 3-functional or more than 3-functional, such astrimesic acid trichloride, cyanuric acid trichloride,3,3′,4,4′-benzophenone-tetracarboxylic acid tetrachloride,1,4,5,8-naphthalenetetracarboxylic acid tetrachloride or pyromelliticacid tetrachloride, in amounts of 0.01 to 1.0 mol % (based on thedicarboxylic acid dichlorides employed), or phenols which are3-functional or more than 3-functional, such as phloroglucinol,4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptene,2,4,4-trimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptane,1,3,5-tri-(4-hydroxyphenyl)-benzene, 1,1,1-tri-(4-hydroxyphenyl)-ethane,tri-(4-hydroxyphenyl)-phenylmethane,2,2-bis[4,4-bis(4-hydroxy-phenyl)-cyclohexyl]-propane,2,4-bis(4-hydroxyphenyl-isopropyl)-phenol,tetra-(4-hydroxyphenyl)-methane,2,6-bis(2-hydroxy-5-methyl-benzyl)-4-methyl-phenol,2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane,tetra-(4-[4-hydroxyphenyl-isopropyl]-phenoxy)-methane or1,4-bis[4,4′-dihydroxytri-phenyl)-methyl]-benzene, in amounts of 0.01 to1.0 mol %, based on the diphenols employed. Phenolic branching agentscan be initially introduced into the reaction vessel with the diphenols,and acid chloride branching agents can be introduced together with theacid dichlorides.

[0072] The content of carbonate structural units in the thermoplasticaromatic polyester-carbonates can vary as desired. The content ofcarbonate groups is preferably up to 100 mol %, in particular up to 80mol %, particularly preferably up to 50 mol %, based on the sum of estergroups and carbonate groups. Both the ester and the carbonate content ofthe aromatic polyester-carbonates can be present in the polycondensatein the form of blocks or in random distribution.

[0073] The relative solution viscosity (η_(rel)) of the aromaticpolycarbonates and polyester-carbonates is in the range from 1.18 to 1.4(measured on solutions of 0.5 g polycarbonate or polyester-carbonate in100 ml methylene chloride solution at 25° C.).

[0074] The thermoplastic aromatic polycarbonates andpolyester-carbonates can be employed by themselves or in any desiredmixture with one another.

[0075] Component B

[0076] Component B comprises one or more graft polymers of

[0077] B.1 5 to 95, preferably 30 to 90 wt. % of at least one vinylmonomer on

[0078] B.2 95 to 5, preferably 70 to 10 wt. % of one or more graft baseswith glass transition temperatures of <10° C., preferably <0° C.,particularly preferably <−20° C.

[0079] The graft base B.2 in general has an average particle size (d₅₀value) of 0.05 to 10 μm, preferably 0.1 to 5 μm, particularly preferably0.2 to 1 μm.

[0080] Monomers B. 1 are preferably a mixture of

[0081] B.1.1 50 to 99 parts by wt. of vinylaromatics and/orvinylaromatics substituted on the nucleus (such as, for example andpreferably, styrene, α-methylstyrene and p-methylstyrene) and/ormethacrylic acid (C₁-C₈)-alkyl esters (such as, for example andpreferably, methyl methacrylate and ethyl methacrylate) and

[0082] B.1.2 1 to 50 parts by wt. of vinyl cyanides (unsaturatednitriles, such as, for example and preferably, acrylonitrile andmethacrylonitrile) and/or (meth)acrylic acid (C₁-C₈)-alkyl esters (suchas, for example and preferably, methyl methacrylate, n-butyl acrylateand t-butyl acrylate) and/or derivatives (such as, for example andpreferably, anhydrides and imides) of unsaturated carboxylic acids (forexample and preferably maleic anhydride and N-phenyl-maleimide).

[0083] Preferred monomers B.1.1 are chosen from at least one of themonomers styrene, α-methylstyrene and methyl methacrylate, and preferredmonomers B.1.2 are chosen from at least one of the monomersacrylonitrile, maleic anhydride and methyl methacrylate.

[0084] Particularly preferred monomers are B.1.1 styrene and B.1.2acrylonitrile.

[0085] Graft bases B.2 which are suitable for graft polymers B are, forexample, diene rubbers, EP(D)M rubbers, that is to say those based onethylene/propylene and optionally diene, and acrylate, polyurethane,silicone and ethylene/vinyl acetate rubbers.

[0086] Preferred graft bases B.2 are diene rubbers (e.g. based onbutadiene, isoprene etc.) or mixtures of diene rubbers or copolymers ofdiene rubbers or mixtures thereof with further copolymerizable monomers(e.g. according to B.1.1 and B.1.2), with the proviso that the glasstransition temperature of component B.2 is below <10° C., preferably <0°C., particularly preferably <−10° C.

[0087] Pure polybutadiene rubber is particularly preferred.

[0088] Particularly preferred polymers B are ABS polymers (emulsion,bulk and suspension ABS) such as are described e.g. in DE-A 2 035 390(=U.S. Pat. No. 3,644,574) or in DE-A 2 248 242 (=GB-A 1 409 275) and inUllmann, Enzyklopädie der Technischen Chemie, vol. 19 (1980), p. 280 etseq. The gel content of graft base B.2 is in general at least 30 wt. %,preferably at least 40 wt. % (measured in toluene).

[0089] Graft copolymers B can be prepared by free-radicalpolymerization, e.g. by emulsion, suspension, solution or bulkpolymerization, preferably by emulsion or bulk polymerization.

[0090] Emulsion ABS and bulk ABS are particularly preferred as componentB.

[0091] Suitable graft rubbers are, in particular, also those ABSpolymers which are prepared by redox initiation with an initiator systemof organic hydroperoxide and ascorbic acid in accordance with U.S. Pat.No. 4,937,285.

[0092] Suitable acrylate rubbers according to B.2 of polymers B arepreferably polymers of acrylic acid alkyl esters, optionally with up to40 wt. %, based on B.2, of other polymerizable, ethylenicallyunsaturated monomers. Preferred polymerizable acrylic acid estersinclude C₁-C₈-alkyl esters, for example the methyl, ethyl, butyl,n-octyl and 2-ethylhexyl ester, and mixtures of these monomers.

[0093] For crosslinking, monomers with more than one polymerizabledouble bond can be copolymerized. Preferred examples of crosslinkingmonomers are esters of unsaturated monocarboxylic acids having 3 to 8 Catoms and unsaturated monohydric alcohols having 3 to 12 C atoms orsaturated polyols having 2 to 4 OH groups and 2 to 20 C atoms, such ase.g. ethylene glycol dimethacrylate and allyl methacrylate;polyunsaturated heterocyclic compounds, such as e.g. trivinyl andtriallyl cyanurate; polyfunctional vinyl compounds, such as di- andtrivinylbenzenes; and also triallyl phosphate and diallyl phthalate.

[0094] Preferred crosslinking monomers are allyl methacrylate, ethyleneglycol dimethacrylate, diallyl phthalate and heterocyclic compoundswhich contain at least 3 ethylenically unsaturated groups.

[0095] Particularly preferred crosslinking monomers are the cyclicmonomers triallyl cyanurate, triallyl isocyanurate,triacryloylhexahydro-s-triazine and triallylbenzenes. The amount ofcrosslinking monomers is preferably 0.02 to 5, in particular 0.05 to 2wt. %, based on graft base B.2.

[0096] In the case of cyclic crosslinking monomers with at least 3ethylenically unsaturated groups, it is advantageous to limit the amountto less than 1 wt. % of graft base B.2.

[0097] Preferred “other” polymerizable, ethylenically unsaturatedmonomers which can optionally be used for the preparation of graft baseB.2, in addition to the acrylic acid esters, are e.g. acrylonitrile,styrene, α-methylstyrene, acrylamides, vinyl C₁-C₆-alkyl ethers, methylmethacrylate and butadiene. Preferred acrylate rubbers as graft base B.2are emulsion polymers which have a gel content of at least 60 wt. %.

[0098] Further suitable graft bases according to B.2 are siliconerubbers with grafting-active sites, such as are described in DE-A 3 704657, DE-A 3 704 655, DE-A 3 631 540 and DE-A 3 631 539.

[0099] The gel content of graft base B.2 is determined at 25° C. in asuitable solvent (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I andII, Georg Thieme-Verlag, Stuttgart 1977).

[0100] The average particle size d₅₀ is the diameter above and belowwhich in each case 50 wt. % of the particles lie. It can be determinedby means of ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid,Z. und Z. Polymere 250 (1972), 782-1796).

[0101] Component C

[0102] The moulding compositions according to the invention comprise asflameproofing agent (C) at least one halogen-free phosphorus compound oflow volatility.

[0103] Preferred phosphorus compounds are those of the general formula(IV)

[0104] wherein

[0105] R¹, R², R³ and R⁴ independently of one another in each casedenote C₁- to C₈-alkyl, or C₅- to C₆-cycloalkyl, C₆- to C₂₀-aryl or C₇-to C₁₂-aralkyl, in each case optionally substituted by alkyl, preferablyC₁-C₄-alkyl,

[0106] n independently of one another, denotes 0 or 1,

[0107] N denotes a number between 0.5 and 30 and

[0108] X denotes a mono- or polynuclear aromatic radical having 6 to 30C atoms or a linear or branched aliphatic radical having 2 to 30 Catoms, which can be OH-substituted and can contain up to 8 ether bonds.

[0109] Preferably, R¹, R², R³ and R⁴ independently of one anotherrepresent C₁-C₄-alkyl, phenyl, naphthyl or phenyl-C₁-C₄-alkyl. Thearomatic groups R¹, R², R³ and R⁴ can in their turn be substituted byalkyl groups, preferably C₁-C₄-alkyl. Particularly preferred arylradicals are cresyl, phenyl, xylenyl, propylphenyl or butylphenyl.

[0110] X in the formula (IV) preferably denotes a mono- or polynucleararomatic radical having 6 to 30 C atoms. This is preferably derived fromdiphenols of the formula (I). In particular, X represents

[0111] n in the formula (IV) is preferably 1.

[0112] N can assume values from 0.5 to 30, preferred values are from 0.5to 10, in particular 0.7 to 5. Mixtures of different phosphatesaccording to formula (IV) can also be employed as component C accordingto the invention. In this case N can assume the abovementioned values asaverage values. The mixtures can also comprise monophosphorus compounds(N=0).

[0113] Monophosphorus compounds of the formula (IV) are, in particular,tributyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenylcresyl phosphate, diphenyl octyl phosphate, diphenyl 2-ethylcresylphosphate, tri-(isopropylphenyl) phosphate, methylphosphonic aciddimethyl ester, methylphosphonic acid diphenyl ester, phenylphosphonicacid diethyl ester, triphenylphosphine oxide or tricresylphosphineoxide. Triphenyl phosphate is a particularly preferred monophosphoruscompound.

[0114] The average N values can be determined by determining thecomposition of the phosphate mixture (molecular weight distribution) bymeans of suitable methods 1 5 (gas chromatography (GC), high pressureliquid chromatography (HPLC), gel permeation chromatography (GPC)) andcalculating the mean values for N therefrom.

[0115] The use of phosphorus compounds of the general formula (V)

[0116] wherein

[0117] R¹, R², R³ and R⁴ in each case independently of one anotherdenote C₁-C₈-alkyl and/or optionally alkyl-substituted C₅-C₆-cycloalkyl,C₆-C₁₀-aryl or C₇-C₁₂-aralkyl,

[0118] n independently of one another, denotes 0 or 1, preferably 1,

[0119] q independently of one another, denotes 0, 1, 2, 3 or 4,preferably 0, 1 or 2,

[0120] N denotes a number between 0.5 and 30, preferably between 0.5 and10, in particular between 0.7 and 5,

[0121] R⁵ and R⁶ independently of one another denote C₁-C₄-alkyl,preferably methyl, and

[0122] Y denotes C₁-C₇-alkylidene, C₁-C₇-alkylene, C₅-C₁₂-cycloalkylene,C₅-C₁₂-cycloalkylidene, —O—, —S—, —SO—, SO₂ or —CO—,

[0123] also proves to be particularly advantageous.

[0124] Those compounds of the general formula (V) which are derived frombisphenol A or methyl-substituted derivatives thereof are particularlypreferred.

[0125] The phosphorus compounds according to the general formula (IV)are known (cf. e.g. EP-A 363 608 and EP-A 640 655) or can be prepared byknown methods in an analogous manner (e.g. Ullmanns Encyklopädie dertechnischen Chemie, vol. 18, p. 301 et seq. 1979; Houben-Weyl, Methodender organischen Chemie, vol. 12/1, p. 43; and Beilstein vol. 6, p. 177).=p Other halogen-free phosphorus compounds of low volatility can also beemployed as flameproofing component (C), and in particular either bythemselves or in any desired mixture with compounds of the generalformula (IV). Possible such halogen-free phosphorus compounds are, inparticular, compounds from the group consisting of phosphazenes andphosphonate-amines.

[0126] Phosphonate-amines are compounds of the formula (VI)

A_(3−y)-NB¹ _(y)   (VI)

[0127] in which

[0128] A represents a radical of the formula (VIa)

[0129] R¹¹ and R¹² independently of one another represent C₁-C₁₀-alkylor represent unsubstituted or substituted C₆-C₁₀-aryl,

[0130] R¹³ and R¹⁴ independently of one another represent C₁-C₁₀-alkylor unsubstituted or substituted C₆-C₁₀-aryl,

[0131] y denotes the numerical values 0, 1 or 2 and

[0132] B¹ independently represents hydrogen, C₂-C₈-alkyl orunsubstituted or substituted C₆-C₁₀-aryl.

[0133] B¹ independently preferably represents hydrogen, ethyl, n- oriso-propyl or unsubstituted or C₁-C₄-alkyl-substituted C₆-C₁₀-aryl, inparticular phenyl or naphthyl.

[0134] Alkyl in R¹¹, R¹², R¹³ and R¹⁴ independently preferablyrepresents methyl, ethyl, n-propyl, iso-propyl, n-, iso-, sec- ortert-butyl, pentyl or hexyl.

[0135] C₆-C₁₀-Aryl in R¹¹, R¹², R¹³ and R¹⁴ independently preferablyrepresents phenyl, naphthyl or binaphthyl.

[0136]5,5,5′,5′,5″,5″-Hexamethyltris(1,3,2-dioxaphosphorinane-methane)amino-2,2′,2″-trioxideof the formula (VI-a-1)

[0137] (test product XPM 1000 of Solutia Inc., St. Louis, USA)

[0138] may be mentioned by way of example and as preferred.

[0139] The preparation of the phosphonate-amines is described, forexample, in U.S. Pat. Specification No. 5,844,028.

[0140] Phosphazenes are compounds of the formulae (VIIa) and/or (VIb)

[0141] wherein

[0142] R is in each case identical or different and represents C₁- toC₆-alkyl or C₁-C₈-alkoxy, or C₅- to C₆-cycloalkyl, C₆- to C₂₀-aryl,preferably phenyl or naphthyl, C₆- to C₂₀-aryloxy, preferably phenoxy ornaphthyloxy, or C₇- to C₁₂-aralkyl, preferably phenyl-C₁-C₄-alkyl, ineach case optionally substituted by alkyl, preferably C₁-C₄-alkyl, and

[0143] k represents 0 or a number from 1 to 15, preferably a number from1 to 10.

[0144] There may be mentioned by way of example and as preferred:

[0145] propoxyphosphazene, phenoxyphosphazene andmethylphenoxyphosphazene.

[0146] Phenoxyphosphazene is particularly preferred.

[0147] Phosphazenes and their preparation are described, for example, inEP-A 728 811, DE-A-1 961668 and WO 97/40092.

[0148] Component D

[0149] The compositions according to the invention can also comprisefluorinated polyolefins as antidripping agents as component D.

[0150] Fluorinated polyolefins are generally known (cf. e.g. EP-A 640655). A commercially available product is, for example, Teflon® 30 Nfrom DuPont.

[0151] The fluorinated polyolefins can be employed either in the pureform or in the form of a coagulated mixture of emulsions of thefluorinated polyolefins with emulsions of graft polymers (B) or with anemulsion of a copolymer, preferably based on styrene/acrylonitrile, thefluorinated polyolefin being mixed as an emulsion with an emulsion ofthe graft polymer or copolymer and the mixture then being coagulated.

[0152] The fluorinated polyolefins can furthermore be employed as aprecompound with graft polymer (B) or a copolymer based on, preferably,styrene/acrylonitrile. The fluorinated polyolefins are mixed as a powderwith a powder or granules of the graft polymer or copolymer and themixture is compounded in the melt, in general at temperatures of 200 to330° C., in conventional units, such as internal kneaders, extruders ortwin-shaft screws.

[0153] The fluorinated polyolefins can also be employed in the form of amasterbatch, which is prepared by emulsion polymerization of at leastone monoethylenically unsaturated monomer in the presence of an aqueousdispersion of the fluorinated polyolefin. Preferred monomer componentsare styrene, acrylonitrile and mixtures thereof. The polymer is employedas a free-flowing powder, after acid precipitation and subsequentdrying.

[0154] The coagulates, precompounds and masterbatches conventionallyhave solids contents of fluorinated polyolefin of 5-95 wt. %, preferably7 to 60 wt. %.

[0155] Component E

[0156] The compositions according to the invention can also comprisefurther polymers or mixtures of polymers as component (E).

[0157] Suitable polymers are, preferably vinyl (co)polymers (E.1) of atleast one monomer from the group consisting of vinylaromatics, vinylcyanides (unsaturated nitriles), (meth)acrylic acid (C₁-C₈)-alkylesters, unsaturated carboxylic acids and derivatives (such as anhydridesand imides) of unsaturated carboxylic acids. Particularly suitablepolymers are (co)polymers of

[0158] E.1.1 50 to 99, preferably 60 to 90 parts by wt. ofvinylaromatics and/or vinylaromatics substituted on the nucleus (suchas, for example and preferably, styrene, cc-methylstyrene andp-methylstyrene) and/or methacrylic acid (C₁-C₈)-alkyl esters (such as,for example and preferably, methyl methacrylate and ethyl methacrylate)and

[0159] E.1.2 1 to 50, preferably 10 to 40 parts by wt. of vinyl cyanides(unsaturated nitriles), such as, for example and preferably,acrylonitrile and methacrylonitrile, and/or (meth)acrylic acid(C₁-C₈)-alkyl esters (such as, for example and preferably, methylmethacrylate, n-butyl acrylate and t-butyl acrylate) and/or unsaturatedcarboxylic acids (such as maleic acid) and/or derivatives (such asanhydrides and imides) of unsaturated carboxylic acids (for example andpreferably maleic anhydride and N-phenyl-maleimide).

[0160] (Co)polymers E.1 are resinous, thermoplastic and rubber-free.

[0161] Copolymers of E.1.1 styrene and E.1.2 acrylonitrile areparticularly preferred.

[0162] The (co)polymers according to E.1 are known and can be preparedby free-radical polymerization, in particular by emulsion, suspension,solution or bulk polymerization. The (co)polymers according to componentE.1 preferably have molecular weights M_(W) (weight-average, determinedby light scattering or sedimentation) of between 15,000 and 200,000.

[0163] Polyalkylene terephthalates (E.2) such as are described inEP-A-841 187 are furthermore suitable.

[0164] Polyalkylene terephthalates which have been prepared fromterephthalic acid and/or reactive derivatives thereof (e.g. dialkylesters thereof) and ethylene glycol and/or butane- 1,4-diol, and alsomixtures of these polyalkylene terephthalates are preferred.

[0165] Component F

[0166] Inorganic materials, in particular those which lead to animprovement in the flame resistance of the polycarbonate mouldingcompositions in low concentrations, can moreover be added to thepolycarbonate composition. All finely ground inorganic materials arepossible in principle. These can have e.g. a particle-, flake- orfibre-like character. Examples which may be mentioned at this point arechalk, quartz powder, titanium dioxide, silicates/aluminosilicates, suchas e.g. talc, wollastonite, mica/clay stratum minerals, montmorillonite,in particular also in an organophilic form modified by ion exchange,kaolin, zeolites and vermiculite, as well as aluminium oxide, silica,magnesium hydroxide, aluminium hydroxide and glass fibres/glass flakes.Mixtures of various inorganic materials can also be employed.

[0167] The inorganic materials can be surface-treated, e.g. silanized,in order to ensure better compatibility with the polymers.

[0168] The inorganic materials are employed in concentrations of 0 to 10wt. %, preferably 0 to 5 wt. %, in particular 0 to 3 wt. %, based on thetotal composition.

[0169] Inorganic materials with a flake-like character are preferablyemployed, such as e.g. talc, mica/clay stratum minerals,montmorillonite, in particular also in an organophilic form modified byion exchange, kaolin and vermiculite.

[0170] Talc is particularly preferred.

[0171] Talc is understood as meaning a naturally occurring orsynthetically prepared talc.

[0172] Pure talc has the chemical composition 3 MgO.4SiO₂.H₂O and thushas an MgO content of 31.9 wt. %, an SiO₂ content of 63.4 wt. % and acontent of chemically bonded water of 4.8 wt. %. It is a silicate with alaminar structure.

[0173] Naturally occurring talc materials in general do not have theabovementioned ideal composition, since they are contaminated by partialreplacement of the magnesium by other elements, by partial replacementof silicon by e.g. aluminium and/or by fusions with other minerals, suchas e.g. dolomite, magnesite and chlorite. These contaminated naturallyoccurring talc powders can also be employed in the moulding compositionsaccording to the invention, but talc types of high purity are preferred.These are characterized by an MgO content of 28 to 35 wt. %, preferably30 to 33 wt. %, particularly preferably 30.5 to 32 wt. %, and an SiO₂content of 55 to 65 wt. %, preferably 58 to 64 wt. %, particularlypreferably 60 to 62.5 wt. %. Preferred talc types are furthermoredistinguished by an A1₂O₃ content of less than 5 wt. %, particularlypreferably less than 1 wt. %, in particular less than 0.7 wt. %.

[0174] The use of talc in the form of finely ground types with anaverage maximum particle size d₅₀ of <20 μm, preferably <10 μm,particularly preferably <5 μm, very particularly preferably <2.5 μm isadvantageous in particular.

[0175] As preferred inorganic components there may furthermore bementioned very finely divided (nanoscale) inorganic compounds of one ormore metals of main groups 1 to 5 or sub-groups 1 to 8 of the periodictable, preferably of main groups 2 to 5 or sub-groups 4 to 8,particularly preferably of main groups 3 to 5 or sub-groups 4 to 8, withthe elements oxygen, sulfur, boron, phosphorus, carbon, nitrogen,hydrogen and/or silicon.

[0176] Preferred compounds are, for example, oxides, hydroxides,hydrated/basic oxides, sulfates, sulfites, sulfides, carbonates,carbides, nitrates, nitrites, nitrides, borates, silicates, phosphatesand hydrides.

[0177] Particularly preferred very finely divided inorganic compoundsare, for example, TiN, TiO₂, SnO₂, WC, ZnO, Al₂O₃, AlO(OH), ZrO₂, SiO₂,iron oxides, BaSO₄, vanadium oxides, zinc borate and silicates, such asAl silicates and Mg silicates. Mixtures and/or doped compounds can alsobe used. These nanoscale particles can be modified on the surface withorganic molecules.

[0178] Nanoscale AlO(OH) is particularly preferred.

[0179] The average particle diameters of the nanoscale inorganicmaterials are less than 200 nm, preferably less than 150 nm, inparticular 1 to 100 nm.

[0180] Particle size and particle diameter always means the averageparticle diameter d₅₀, determined by ultracentrifuge measurements by themethod of W. Scholtan et al., Kolloid-Z. und Z. Polymere 250 (1972), p.782 to 796.

[0181] The nanoscale inorganic compounds can be in the form of powders,pastes, sols, dispersions or suspensions. Powders can be obtained byprecipitation from dispersions, sols or suspensions.

[0182] Component G

[0183] The moulding compositions according to the invention can moreovercomprise conventional polymer additives, such as e.g. antidrippingagents which differ from component (D), flameproofing agents whichdiffer from component (C), lubricants and mould release agents,nucleating agents, antistatics which differ from component H,stabilizers, dyestuffs and pigments and fillers and reinforcingsubstances in an active concentration.

[0184] Component H

[0185] The moulding compositions according to the invention comprise asthe antistatic at least one polyalkylene ether of the general formula(VIII)

R₁—O—(C_(x)H_(2x)O)_(n)—R₂   (VIII)

[0186] In formula (VIII)

[0187] R₁ and R₂ independently of one another represent hydrogen, asaturated or unsaturated hydrocarbon radical or an acyl radical,

[0188] x represents the numbers 2 or 3, wherein x can assume differentvalues in the same molecule and the content of monomers where x=3 is 60to 100 wt. %, preferably 70 to 100 wt. %, based on the mass of theantistatic according to component H, and

[0189] n represents a number which is chosen such that the averagemolecular weight of the polyalkylene ether (determined by measurement ofthe OH number) is ≧2,000 g mol⁻¹, preferably ≧3,000 g mol⁻¹, inparticular ≧3,500 g mol⁻¹.

[0190] In polyalkylene ethers of the formula (VIII) which simultaneouslycontain monomer units where x=2 and x=3, that is to say both ethyleneoxide and propylene oxide units, these can be arranged in thepolyalkylene ether chain both in random distribution and in blocks ofpure polyethylene oxide, pure polypropylene oxide and/or randomly mixedpolyethylene-propylene oxide. Linear triple-block copolymers which arebuilt up from homopolymer blocks are preferred.

[0191] As comonomer units polymerized-in the polyalkylene ethers canadditionally contain: diols and alcohols of higher functionality, e.g.glycerol, neopentylglycol and butanediol, and/or aromatic diphenols,such as are described in the case of formula (I), e.g. bisphenol A,resorcinol and hydroquinone.

[0192] Preferred polyalkylene ethers are pure polypropylene oxides ortriple-block copolymers of the general formula X—Y—X with a centralpolypropylene oxide block Y and terminal polyethylene oxide blocks X.The content of the two terminal polyethylene blocks X taken together inthe triple-block copolymer can be 0 to 40, preferably 0 to 30, inparticular 0 to 20 wt. %, based on the mass of the block copolymer. Thecontent of the central polypropylene oxide block Y is accordingly 60 to100, preferably 70 to 100, in particular 80 to 100 wt. %. Thetriple-block copolymers are prepared in a manner known per se bypolymerization, wherein a central polypropylene oxide block Y is firstprepared and in each case a block of ethylene oxide units is added on toits two ends (see e.g. N. Schönfeld, GrenzflaichenaktiveEthylenoxid-Addukte, Wissenschaftliche Verlagsgesellschaft mbH,Stuttgart, 1976, pages 53 et seq.). Preferred triple-block copolymersand their preparation are also described in EP-A-0 135 801 and EP-A-0018 591.

[0193] To intensify their antistatic action, the polyalkylene ethersemployed as component (H) can also be reacted with agents which formfree radicals in accordance with the process described in EP-A-0 278 348and U.S. Pat. No. 4,920,166. Possible substances which form freeradicals are the commercially available compounds known as initiatorsfor free-radical polymerization, and all other compounds whichdissociate to form free radicals sufficiently rapidly at temperatures ofbetween 20 and 200° C. Thus, for example, it is possible to employdiacyl peroxides, such as dibenzoyl peroxide, substituted dibenzoylperoxides and dilauroyl peroxide, acylsulfonyl peroxides, such asacetylcyclohexanesulfonyl peroxide, peroxydicarbonates, such asdicyclohexyl and di-tert-butyl peroxydicarbonate, acyl peresters, suchas tert-butyl perpivalate and tert-butyl perbenzoate, dialkyl peroxides,such as dicumyl and di-tert-butyl peroxide, hydroperoxides, such ascumyl hydroperoxide and tert-butyl hydroperoxide, and other peroxycompounds, as well as aliphatic and araliphatic azo compounds. Preferredagents which form free radicals dissociate sufficiently rapidly attemperatures of 60 to 140° C., e.g. azodiisobutyronitrile, di-tert-butylperoxide, dibenzoyl peroxide, tert-butyl perbenzoate, dicumyl peroxideand 1,3-bis-(tert-butylperoxyisopropyl)benzene. Dibenzoyl peroxide isparticularly preferably used.

[0194] The polyalkylene ethers according to the invention modified byreaction with agents which form free radicals can be prepared by simplystirring the agent which forms free radicals with the particularpolyalkylene ether at temperatures of between 50 and 150° C. The amountof agent which forms free radicals employed here, based on the amount ofpolyalkylene ether, is 0.05 to 5 wt. %, preferably 0.1 to 2.0 wt. % andparticularly preferably 0.25 to 1.0 wt. %.

[0195] Because of their relatively low plasticizer action and theirrelatively low volatility, but not because of their relatively highefficiency as an antistatic, those polyalkylene ethers with anumber-average molecular weight of ≧2,000 g mol⁻¹, preferably ≧3,000 gmol⁻¹, in particular ≧3,500 g mol⁻¹ are preferably employed.

[0196] The moulding compositions according to the invention comprisingcomponents A to H and optionally further additives are prepared bymixing the particular constituents in a known manner and subjecting themixture to melt compounding or melt extrusion at temperatures of 200° C.to 300° C. in conventional units, such as internal kneaders, extrudersand twin-shaft screws.

[0197] The mixing of the individual constituents can be carried out in aknown manner both successively and simultaneously, and in particularboth at about 20° C. (room temperature) and at a higher temperature.

[0198] On the basis of their excellent flame resistance, their goodmechanical and thermal properties and on the basis of their goodprocessing properties, the thermoplastic moulding compositions accordingto the invention are suitable for the production of all types of shapedarticles. The shaped articles can in principle be prepared by all knownprocesses, e.g. by injection moulding and extrusion. The mouldingcompositions are preferably suitable for the production of shapedarticles in the injection moulding process.

[0199] Preferred examples of shaped articles which can be produced are:housing components of all types, e.g. for domestic appliances, such asjuice presses, coffee machines and mixers; for electric motors, such asin lawnmowers, drilling machines etc., and for office machines, such asmonitors, (portable) computers, printers and copiers. Further possiblefields of use are mouldings, extruded profiles or sheets for the motorvehicle/railway vehicle/aircraft sector (e.g. interior linings). Themoulding compositions can also be employed for uses in electricalengineering, e.g. for switches, sockets and circuit boards, and fordistributor and electricity meter boxes.

[0200] The invention also provides processes for the preparation of themoulding compositions according to the invention, their use for theproduction of shaped articles of all types and these shaped articlesthemselves.

EXAMPLES

[0201] Component A.1

[0202] Polycarbonate based on bisphenol A with a relative solutionviscosity of 1.25, measured in methylene chloride at 25° C. and in aconcentration of 0.5 g/100 ml.

[0203] Component A.2

[0204] Polycarbonate based on bisphenol A with a relative solutionviscosity of 1.24, measured in methylene chloride at 25° C. and in aconcentration of 0.5 g/100 ml.

[0205] Component B

[0206] Graft polymer prepared by emulsion polymerization of 45 parts bywt. styrene and acrylonitrile in a weight ratio of 72:28 on 55 parts bywt. of a particulate crosslinked polybutadiene rubber (average particlediameter d₅₀=0.3 to 0.4 μm).

[0207] Component C.1

[0208] Resorcinol-based oligophosphate

[0209] Component C.2

[0210] Bisphenol A-based oligophosphate

[0211] For determination of the number-average N values stated forcomponents C.1 and C.2, the contents of the oligomeric phosphates werefirst determined by HPLC measurements: Column type: LiChrosorp RP-8Eluent in gradient: acetonitrile/water 50:50 to 100:0 Concentration: 5mg/ml

[0212] The number-weighted N mean values were then calculated from thecontents of the individual components (mono- and oligophosphate) byknown methods.

[0213] Component D

[0214] The polytetrafluoroethylene preparation (D) used here is preparedby coprecipitation of a mixture of aqueous emulsions of graft polymer(B) and a tetrafluoroethylene polymer. The weight ratio of graft polymer(B) to tetrafluoroethylene polymer in the coagulate is 90 wt. % to 10wt. %. The tetrafluoroethylene polymer emulsion has a solids content of60 wt. %, and the average PTFE particle diameter is between 0.05 and 0.5μm. The graft polymer emulsion has a solids content of 34 wt. % and anaverage latex particle diameter of 0.3 to 0.4 μm.

[0215] To prepare (D), the emulsion of the tetrafluoroethylene polymer(Teflon 30 N from DuPont) is mixed with the emulsion of graft polymer(B) and the mixture is stabilized with 1.8 wt. %, based on the polymersolid, of phenolic antioxidants. The mixture is coagulated with anaqueous solution of MgSO₄ (Epsom salt) and acetic acid at pH 4 to 5 at85 to 95° C. and filtered, and the residue is washed until practicallyfree from electrolytes, subsequently freed from most of the water bycentrifugation and then dried at 100° C. to give a powder.

[0216] Component E

[0217] Styrene/acrylonitrile copolymer with a styrene/acrylonitrileweight ratio of 72:28 and a limiting viscosity of 0.55 dl/g (measurementin dimethylformamide at 20° C.).

[0218] Component F.1

[0219] Pural 200: nanoscale AlO(OH) with a boehmite structure fromCondea Chemie GmbH (Hamburg, Germany).

[0220] Component F.2

[0221] Naintsch A3: very finely ground highly pure talc from NaintschMineralwerke GmbH (Graz, Austria).

[0222] Component G.1

[0223] Phosphite stabilizer

[0224] Component G.2

[0225] Pentaerythritol tetrastearate as a mould release agent

[0226] Component H.1

[0227] Block copolymer with the structure X—(XY)—Y—(XY)—X with a centralpolypropylene oxide block Y, randomly mixed propylene oxide/ethyleneoxide blocks (XY) adjacent thereto and terminal polyethylene oxideblocks X. The propylene oxide content of the block copolymer is 51 wt.%; the number-average molecular weight is approx. 2,000 g mol⁻¹ (OHnumber=58).

[0228] Component H.2

[0229] Modified linear polypropylene glycol: To prepare component H.2,1.0 kg of a linear polypropylene glycol with a number-average molecularweight of approx. 2,000 g mol⁻¹ (OH number=56) is degassed in vacuo at120° C. and subsequently saturated with nitrogen. After addition of 6.6g dibenzoyl peroxide at a temperature of <40° C., the resulting mixtureis reacted under nitrogen for 8 hours at 80-85° C.

[0230] Component H.3

[0231] Triple-block copolymer with the structure X—Y—X with a centralpolypropylene oxide block Y and terminal polyethylene oxide blocks X.The propylene oxide content of the block copolymer is 70.3 wt. %; thenumber-average molecular weight is approx. 4,000 g mol⁻¹ (OH number=29).

[0232] Component H.4

[0233] Triple-block copolymer with the structure X—Y—X with a centralpolypropylene oxide block Y and terminal polyethylene oxide blocks X.The propylene oxide content of the block copolymer is 86.7 wt. %; thenumber-average molecular weight is approx. 4,000 g mol⁻¹ (OH number=27).

[0234] Preparation and Testing of the Moulding Compositions According tothe Invention

[0235] Components A to H were mixed with a 3 1 internal kneader or inthe case of examples 8-10 and comparison example V6 with a laboratoryextruder (ZSK 25, Werner & Pfleiderer) at a material temperature of 240°C., a throughput of 15 kg/h and a screw rotation frequency of 200 rpm.The shaped articles were produced on an injection moulding machine (typeArburg 270E) at 240° C.

[0236] The notched impact strength (a_(k)) is determined at roomtemperature in accordance with ISO 180-1A.

[0237] The Vicat B 120 temperature is determined in accordance with ISO306 at a heating up rate of 120 K/h and a stamp load of 50 N.

[0238] The flame resistance is determined in accordance with UL94V,evaluated on bars with a thickness of 1.6 mm. A flame-resistant materialin the context of the present invention exists if the UL94V test at awall thickness of 1.6 mm is passed with the rating V-0 or V-1.

[0239] The melt viscosity, as a measure of the flowability duringprocessing in the injection moulding process, is determined inaccordance with DIN 54811 at 260° C. and at a shear rate of 1,000 s⁻¹.

[0240] The MVR is determined in accordance with ISO 1133 at 240° C.using a stamp load of 5 kg.

[0241] The tendency of the plastic towards juicing during injectionmoulding is evaluated with the aid of the results of a TGA analysis. Forthis, approx. 2.5 mg of the moulding compositions compounded asdescribed above are heated up dynamically in a stream of nitrogen (50ml/min) at a rate of 10 K/min, starting from room temperature. Thepercentage weight loss determined at a temperature of 280° C. reachedserves as a measure of the tendency towards bleeding of volatileconstituents of the moulding composition.

[0242] The antistatic properties of the materials are evaluated with theaid of a dust attraction test. For this, circular sheets with a diameterof 80 mm and a thickness of 2 mm are injection moulded using asurface-polished injection mould and immediately thereafter packedindividually in bags of glassine paper. The injection moulding andtesting are separated by a time span of at least one week. In test 1 thecircular sheet is taken out of the paper bag. The surface of the plasticis electrically charged by the friction which arises as a result.Immediately after removal from the bag the circular sheet is kept for 10s in an air atmosphere containing active charcoal dust and is thenevaluated visually. In test 2 the circular sheet is first conditionedfor 24 h at 23° C. and at a relative atmospheric humidity of 80% afterremoval from the paper bag and before the exposure to dust by the methoddescribed above. The active charcoal dust atmosphere is established in adefined manner in that in a 3 1 glass beaker which contains about 50 gactive charcoal dust (Riedel de Haen, Seelze, Germany) and a magneticstirrer core of suitable geometry, the dust is swirled up with amagnetic stirrer. In each case on the one hand the amount of charcoaldust deposited is evaluated both visually and gravimetrically and on theother the appearance of particularly undesirable, non-uniform dustpatterns (“dust figures”) is evaluated visually. The visual evaluationwas in each case made by four independent persons, without these knowingthe allocation of the sheets to the concrete materials. Uniformevaluations were made by all the persons performing the evaluations inall cases. A material is classified as anti-electrostatic in the contextof the present invention if, in test 2, it shows only a low or very lowattraction of dust and shows no dust figures. TABLE 1 Compositions andproperties V1* V2* 1 2 3 Example/ Components A.1 Polycarbonate 68.4 68.468.4 68.4 68.4 B Graft polymer 6.8 6.8 6.8 6.8 6.8 C.1 RDP 10.8 10.810.8 10.8 10.8 D PTFE preparation (10% PTFE) 4.2 4.2 4.2 4.2 4.2 E SAN9.3 9.3 9.3 9.3 9.3 G.1 Stabilizer 0.1 0.1 0.1 0.1 0.1 G.2 Mould releaseagent 0.4 0.4 0.4 0.4 0.4 H.1 Antistatic — 2.0 — — — (M = 2,000 g mol⁻¹,PO = 51%) H.2 Antistatic — — 2.0 — — (M = 2,000 g mol⁻¹, PO = 100%) H.3Antistatic — — — 2.0 — (M = 4,000 g mol⁻¹, PO = 70.3%) H.4 Antistatic —— — — 2.0 (M = 4,000 g mol⁻¹, PO = 86.7%) Properties Vicat B 120 [° C.]95 87 89 90 94 MVR [ml/10 min] 25 38 37 37 37 [240° C./5 kg] AntistaticTendency to attract dust high high low low very properties low (Test 2)Dust figures yes yes no no no

[0243] TABLE 2 Compositions and properties V3* V4* 4 5 6 7 V5* Example/Components A.1 Polycarbonate 68.4 68.4 68.4 68.4 68.4 68.4 68.4 B Graftpolymer 6.8 6.8 6.8 6.8 6.8 6.8 6.8 C.1 RDP 10.8 10.8 10.8 10.8 10.810.8 10.8 D PTFE preparation (10% PTFE) 4.2 4.2 4.2 4.2 4.2 4.2 4.2 ESAN 9.3 9.3 9.3 9.3 9.3 9.3 9.3 F.1 Nanoscale AlO(OH) — — 0.7 — 0.7 0.70.7 G.1 Stabilizer 0.1 0.1 0.1 0.1 0.1 0.1 0.1 G.2 Mould release agent0.4 0.4 0.4 0.4 0.4 0.4 0.4 H.2 Antistatic — 3.0 3.0 — — — — (M = 2,000g mol⁻¹, PO = 100%) H.4 Antistatic — — — 3.0 2.0 3.0 4.0 (M = 4,000 gmol⁻¹, PO = 86.7%) Properties Vicat B 120 [° C.] 94 87 87 92 92 92 91Viscosity [Pa s] 151 125 127 130 138 131 96 [260° C./1000s⁻¹) a_(k) (23°C.) [kJ/m²] 41 41 42 40 45 43 41 UL94 Evaluation at 1.6 mm V-0 V-2 V-0V-1 V-1 V-1 F fire test Juicing Weight loss at 280° C. 1.28 1.57 1.27tendency [%] Antistatic Tendency to attract dust high low low very lowlow very properties low low (Test 1) Dust figures yes no no no no no noAntistatic Tendency to attract dust high very very very very very veryproperties low low low low low low (Test 2) Dust figures yes no no no nono no

[0244] TABLE 3 Compositions and properties V6* 8 9 10 Example/Components A.2 Polycarbonate 65.3 65.3 65.3 65.3 B Graft polymer 7.0 7.07.0 7.0 C.2 BDP 14.6 14.6 14.6 14.6 D PTFE preparation (10% PTFE) 4.64.6 4.6 4.6 E SAN 6.0 6.0 6.0 6.0 F.2 Talc 2.0 2.0 2.0 2.0 G.1Stabilizer 0.1 0.1 0.1 0.1 G.2 Mould release agent 0.4 0.4 0.4 0.4 H.4Antistatic — 1.5 3.0 4.5 (M = 4,000 g mol⁻¹, PO = 86.7%) PropertiesVicat B 120 [° C.] 95 93 92 90 Viscosity [Pa s] 155 139 115 78 [260°C./1000s⁻¹] a_(k) (23° C.) [kJ/m²] 18 24 22 20 UL94 fire test Evaluationat 1.6 mm V-0 V-0 V-0 V-1 Antistatic Tendency to attract dust high highvery very properties low low (Test 1) Dust figures yes yes no noAntistatic Tendency to attract dust high low very very properties lowlow (Test 2) Dust figures yes no no no

[0245] Table 1 shows that by addition of polyalkylene ethers accordingto the invention based on propylene oxide and ethylene oxide tohalogen-free PC/ABS blends which are provided with flame resistance, thetendency of the plastic to attract dust can be significantly reduced(compare comparison example V1 with examples 1-3). As the propyleneoxide content increases, at the same molecular weight the antistaticaction of the polyalkylene ethers increases (compare examples 2 and 3and example 1 and comparison example V2). A polyalkylene ether based onethylene oxide and propylene oxide with a propylene oxide content ofonly 51% (comparison example 2) is evidently not capable ofsignificantly improving the dust attraction properties of theflame-resistant PC/ABS blend. Suitable polyalkylene ethers are both purepolypropylene oxides (example 1) and those polymers which are based onpolypropylene oxide blocks and polyethylene blocks and have thestructure of a triple-block copolymer of the general formula X—Y—X,wherein X represents polyethylene oxide blocks and Y represents apolypropylene oxide block (examples 2 and 3). Those modifiedpolyalkylene ethers which have been reacted at elevated temperatureswith agents which form free radicals are also suitable as an antistatic(example 1). All the polyalkylene ethers mentioned lead to animprovement in the flowability of the plastic and therefore to animproved processability of the material in the injection mouldingprocess. The use of polyalkylene ethers which are distinguished by ahigh molecular weight (e.g. at a level of 4,000 g mol⁻¹) proves to beadvantageous because of the higher heat distortion point and the lowertendency towards juicing (table 2) of the blends provided withanti-electrostatic properties with them. In particular, a high propyleneoxide content of the polyalkylene ether employed also proves to beadvantageous in respect of the heat distortion point of the blendprovided with antistatic properties (cf. examples 2 and 3).

[0246] Tables 2 and 3 show that the addition of the polyalkylene etherssuitable as an antistatic does not have an adverse effect on themechanical properties, such as the notched impact strength. Thesometimes adverse influence of the polyalkylene ether on the flameresistance of the material can be at least partly cancelled out byaddition of small amounts of inorganic materials, such as e.g. nanoscaleAlO(OH) or talc (see e.g. comparison example V3 and V4 and example 4).At very high concentrations of the polyalkylene ether (e.g. ≧4 to 5 wt.%), excellent antistatic properties are indeed observed, but an adequateflame resistance and heat distortion point often (depending on theparticular overall recipe) can no longer be realized under thesecircumstances (comparison example V5).

1. Compositions comprising polycarbonate and/or polyester-carbonate, atleast one impact modifier, at least one phosphorus-containingflameproofing agent chosen from at least one of the substance group ofoligomeric phosphoric acid esters, phosphazenes and phosphonate-aminesand a polyalkylene ether which is optionally modified with agents whichform free radicals and is based on propylene oxide and optionallyethylene oxide, with a propylene oxide content, based on thepolyalkylene ether, of 60 to 100 wt. %, wherein the mouldingcompositions are characterized in that they pass the UL94V test at awall thickness of 1.6 mm with V-0 or V-1.
 2. Compositions comprisingpolycarbonate and/or polyester-carbonate, at least one impact modifier,at least one phosphorus-containing flameproofing agent chosen from atleast one of the substance group of oligomeric phosphoric acid esters,phosphazenes and phosphonate-amines and 0.5 to 3 parts by wt. (based on100 parts by wt. of a composition) of a polyalkylene ether which isoptionally modified with agents which form free radicals and is based onpropylene oxide and optionally ethylene oxide, with a propylene oxidecontent, based on the polyalkylene ether, of 60 to 100 wt. %. 3.Compositions according to claim 1 or 2, comprising 30 to 98 parts by wt.of aromatic polycarbonate and/or polyester-carbonate, 0.5 to 50 parts bywt. of at least one graft polymer, 0.5 to 40 parts by wt. of at leastone phosphorus-containing flameproofing agent chosen from the substancegroups of oligomeric phosphoric acid esters, phosphazenes andphosphonate-amines and 0.05 to 5 parts by wt. of a polyalkylene etherwhich is optionally modified with agents which form free radicals and isbased on propylene oxide and optionally ethylene oxide, with a propyleneoxide content, based on the polyalkylene ether, of 60 to 100 wt. %, thesum of the parts by weight of the components being
 100. 4. Compositionsaccording to claim 1, 2 or 3, comprising 40 to 95 parts by wt. ofaromatic polycarbonate, 1 to 35 parts by wt. of at least one graftpolymer, 1 to 30 parts by wt. of at least one phosphorus-containingflameproofing agent chosen from the substance groups of oligomericphosphoric acid esters, phosphazenes and phosphonate-amines and 0.1 to 4parts by wt. of a polyalkylene ether which is optionally modified withagents which form free radicals and is based on propylene oxide andoptionally ethylene oxide, with a propylene oxide content, based on thepolyalkylene ether, of 60 to 100 wt. %.
 5. Compositions according to oneor more of the preceding claims, comprising 50 to 90 parts by wt. ofaromatic polycarbonate, 2 to 25 parts by wt. of at least one graftpolymer, 2 to 20 parts by wt. of at least one phosphorus-containingflameproofing agent chosen from the substance groups of oligomericphosphoric acid esters, phosphazenes and phosphonate-amines and 0.5 to 3wt. % of a polyalkylene ether which is optionally modified with agentswhich form free radicals and is based on propylene oxide and optionallyethylene oxide, with a propylene oxide content, based on thepolyalkylene ether, of 60 to 100 wt. %.
 6. Compositions according to oneor more of the preceding claims, additionally comprising fluorinatedpolyolefin, optionally as a coagulate, precompound or masterbatch with agraft polymer or a vinyl (co)polymer.
 7. Compositions according to oneor more of the preceding claims, additionally comprising vinyl(co)polymers, polyalkylene terephthalates or mixtures thereof. 8.Compositions according to one or more of the preceding claims,additionally comprising an inorganic material in the form of particles,flakes or fibres.
 9. Compositions according to claim 8, comprising asthe inorganic material talc or a nanoscale material with an averageparticle diameter of ≦200 nm.
 10. Compositions according to one or moreof the preceding claims, comprising further commercially availableadditives.
 11. Compositions according to one or more of the precedingclaims, comprising as the flameproofing agent a phosphorus-containingcompound of the general formula (IV)

wherein R¹, R², R³ and R⁴ independently of one another in each casedenote C₁- to C₈-alkyl, or C₅- to C₆-cycloalkyl, C₆- to C₂₀-aryl or C₇-to C₁₂-aralkyl, in each case optionally substituted by alkyl, preferablyC₁-C₄-alkyl, n independently of one another, denotes 0 or 1, N denotes anumber between 0.5 and 30 and X denotes a mono- or polynuclear aromaticradical having 6 to 30 C atoms or a linear or branched aliphatic radicalhaving 2 to 30 C atoms, which can be OH-substituted and can contain upto 8 ether bonds.
 12. Compositions according to one or more of thepreceding claims, comprising as the flameproofing agent aphosphorus-containing compound of the general formula (V)

wherein R¹, R², R³and in each independently of one another denoteC₁-C₈-alkyl and/or optionally alkyl-substituted C₅-C₆-cycloalkyl,C₆-C₁₀-aryl or C₇-C₁₂-aralkyl, n independently of one another, denotes 0or 1, q independently of one another, denotes 0, 1, 2, 3 or 4, N denotesa number between 0.5 and 30, R⁵ and R⁶ independently of one anotherdenote C₁-C₄-alkyl and Y denotes C₁-C₇-alkylidene, C₁-C₇-alkylene, C₅-C₁₂-cycloalkylene, C₅-C₁₂-cycloalkylidene, —O—, —S—, —SO—, SO₂ or —CO—.13. Compositions according to one or more of the preceding claims,comprising as the flameproofing agent an oligophosphate based onbisphenol A or resorcinol, of the formula

where N is between 0.5 and
 10. 14. Compositions according to one or moreof the preceding claims, comprising as the impact modifier one or moregraft polymers of 5 to 95 wt. % of at least one vinyl monomer on 95 to 5wt. % of at least one graft base with a glass transition temperature of<10° C.
 15. Compositions according to claim 14 with graft polymers basedon diene, EP(D)M, acrylate or silicone rubbers.
 16. Compositionsaccording to claim 15, comprising an emulsion or bulk ABS or mixturesthereof as the impact modifier.
 17. Compositions according to one ormore of the preceding claims, in which the polyalkylene ether is a purepolypropylene oxide which has optionally been reacted with agents whichform free radicals.
 18. Compositions according to claim 17, in which thepolyalkylene ether has the structure of a triple-block copolymer of thegeneral formula X—Y—X, wherein X represents polyethylene oxide blocksand Y represents a polypropylene oxide block.
 19. Compositions accordingto one of claims 17 and 18, in which the polyalkylene ether has anumber-average molecular weight of ≧3,000 g mol⁻¹.
 20. Process for thepreparation of the polycarbonate moulding compositions according to oneor more of the preceding claims, wherein the individual components aremixed and the mixture is compounded at elevated temperature.
 21. Use ofthe polycarbonate moulding compositions according to one or more of thepreceding claims for the production of shaped articles or mouldings ofall types.
 22. Shaped articles or mouldings obtainable from thepolycarbonate moulding compositions according to one or more of thepreceding claims.